Sodium methylsulfinylmethylide

Sodium methylsulfinylmethylide
Names
	Preferred IUPAC name Sodium (methanesulfinyl)methanide
	Other names sodium dimsylate, dimsylsodium, NaDMSYL
Identifiers
CAS Number	15590-23-5 ;
3D model (JSmol)	Interactive image;
Abbreviations	NaDMSO
ChemSpider	8329518 ;
PubChem CID	10154010;
UNII	R6HI470Q52 ;
CompTox Dashboard (EPA)	DTXSID10436194 ;
	InChI InChI=1S/C2H5OS.Na/c1-4(2)3;/h1H2,2H3;/q-1;+1 Key: CWXOAQXKPAENDI-UHFFFAOYSA-N ; InChI=1S/C2H5OS.Na/c1-4(2)3;/h1H2,2H3;/q-1;+1 Key: CWXOAQXKPAENDI-UHFFFAOYAA; Key: CWXOAQXKPAENDI-UHFFFAOYSA-N;
	SMILES [Na+].O=S([CH2-])C;
Properties
Chemical formula	CH3S(O)CH2Na
Molar mass	100.11 g·mol−1
Appearance	White solid, solution in DMSO is green
Solubility in water	decomposes
Solubility	Very soluble in DMSO and many polar organic solvents
Hazards
	Occupational safety and health (OHS/OSH):
Main hazards	May form corrosive NaOH, May be explosive in certain circumstances.
Related compounds
Related compounds	Dimethyloxosulfonium methylide, Dimethyl sulfoxide
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Sodium methylsulfinylmethylide (also called NaDMSO or dimsyl sodium) is the sodium salt of dimethyl sulfoxide. It has the chemical formula C H₃S(O)CH−2Na⁺. This unusual salt has some uses in organic chemistry as a base and nucleophile.

First reported by Corey and Chaykovsky in 1962.^[2] and subsequent usage in organic synthesis reported in 1965 by Corey et al.,^[3] a number of additional uses for this reagent have been identified.^[4]

Preparation

Sodium methylsulfinylmethylide is prepared by heating sodium hydride^[5] or sodium amide^[6] in DMSO^[7]

CH₃S(O)CH₃ + NaH → CH₃S(O)CH−2Na⁺ + H₂

CH₃S(O)CH₃ + NaNH₂ → CH₃S(O)CH−2Na⁺ + NH₃

Reactions

As a base

The pK_a of DMSO is 35, which leads NaDMSO to be a powerful Brønsted base. NaDMSO is used in the generation of phosphorus and sulfur ylides.^[8] NaDMSO in DMSO is especially convenient in the generation of dimethyloxosulfonium methylide and dimethylsulfonium methylide.^[3]^[9]

Reaction with esters

NaDMSO condenses with esters (1) to form β-ketosulfoxides (2), which can be useful intermediates.^[10] Reduction of β-ketosulfoxides with aluminium amalgam gives methyl ketones (3).^[11] Reaction with alkyl halides followed by elimination gives α,β-unsaturated ketones (4). β-ketosulfoxides can also be used in the Pummerer rearrangement to introduce nucleophiles alpha to a carbonyl (5).^[12]

Methylation of sugars

Permethylation of sugars with dimsyl sodium was reported by Hakomori in 1964^[13] This usage is sometimes called Hakomori methylation.

References

↑ "Sodium Hydride in Aprotic Solvents: Look Out".
↑ Corey, E. J.; Chaykovsky, M. (1962). "Methylsulfinylcarbanion". J. Am. Chem. Soc. 84 (5): 866–867. doi:10.1021/ja00864a039.
1 2 Corey, E. J.; Chaykovsky, M. (1965). "Methylsulfinyl Carbanion (CH₃-SO-CH₂⁻). Formation and Applications to Organic Synthesis". J. Am. Chem. Soc. 87 (6): 1345–1353. doi:10.1021/ja01084a033.
↑ Mukulesh Mondal "Sodium methylsulfinylmethylide: A versatile reagent" Synlett 2005, vol. 17, 2697-2698. doi:10.1055/s-2005-917075
↑ Iwai, I.; Ide, J. (1988). "2,3-Diphenyl-1,3-Butadiene". Organic Syntheses{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 6, p. 531.
↑ Kaiser, E. M.; Beard, R. D.; Hauser, C. R. (1973). "Preparation and reactions of the mono- and dialkali salts of dimethyl sulfone, dimethyl sulfoxide, and related compounds". J. Organomet. Chem. 59: 53–64. doi:10.1016/S0022-328X(00)95020-4.
↑ "Preparation of dimsyl sodium".
↑ Romo, D.; Myers, A. I. (1992). "An asymmetric route to enantiomerically pure 1,2,3-trisubstituted cyclopropanes". J. Org. Chem. 57 (23): 6265–6270. doi:10.1021/jo00049a038.
↑ Trost, B. M.; Melvin, L. S., Jr. (1975). Sulfur Ylides: Emerging Synthetic Intermediates. New York: Academic Press. ISBN 0-12-701060-2.{{cite book}}: CS1 maint: multiple names: authors list (link)
↑ Ibarra, C. A; Rodgríguez, R. C; Monreal, M. C. F; Navarro, F. J. G.; Tesoreo, J. M. (1989). "One-pot synthesis of β-keto sulfones and β-keto sulfoxides from carboxylic acids". J. Org. Chem. 54 (23): 5620–5623. doi:10.1021/jo00284a043.
↑ Swenton, J. S.; Anderson, D. K.; Jackson, D. K.; Narasimhan, L. (1981). "1,4-Dipole-metalated quinone strategy to (±)-4-demethoxydaunomycinone and (±)-daunomycinone. Annelation of benzocyclobutenedione monoketals with lithioquinone bisketals". J. Org. Chem. 46 (24): 4825–4836. doi:10.1021/jo00337a002.
↑ Isibashi, H.; Okada, M.; Komatsu, H.; Ikeda, M. S. (1985). "A New Synthesis of Substituted Cyclopentenones by Olefin Cyclization Initiated by Pummerer Reaction Intermediates". Synthesis. 1985 (6/7): 643–645. doi:10.1055/s-1985-31290. S2CID 95643470.
↑ Hakomori, S.-I. (1964). "A Rapid Permethylation of Glycolipid, and Polysaccharide Catalyzed by Methylsulfinyl Carbanion in Dimethyl Sulfoxide". J. Biochem. 55 (2): 205–208. doi:10.1093/oxfordjournals.jbchem.a127869.

External links

"The Dimethyl Sulfoxide (DMSO) Anion — Dimsyl Ion" (PDF). Gaylord Chemical Corporation. October 2007. Archived from the original (PDF) on 2011-07-11.
"Preparation of dimsyl sodium". June 2009.

[1] "Sodium Hydride in Aprotic Solvents: Look Out".

[Corey1962-2] Corey, E. J.; Chaykovsky, M. (1962). "Methylsulfinylcarbanion". J. Am. Chem. Soc. 84 (5): 866–867. doi:10.1021/ja00864a039.

[Corey1965-3] 1 2 Corey, E. J.; Chaykovsky, M. (1965). "Methylsulfinyl Carbanion (CH₃-SO-CH₂⁻). Formation and Applications to Organic Synthesis". J. Am. Chem. Soc. 87 (6): 1345–1353. doi:10.1021/ja01084a033.

[4] Mukulesh Mondal "Sodium methylsulfinylmethylide: A versatile reagent" Synlett 2005, vol. 17, 2697-2698. doi:10.1055/s-2005-917075

[5] Iwai, I.; Ide, J. (1988). "2,3-Diphenyl-1,3-Butadiene". Organic Syntheses{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 6, p. 531.

[6] Kaiser, E. M.; Beard, R. D.; Hauser, C. R. (1973). "Preparation and reactions of the mono- and dialkali salts of dimethyl sulfone, dimethyl sulfoxide, and related compounds". J. Organomet. Chem. 59: 53–64. doi:10.1016/S0022-328X(00)95020-4.

[7] "Preparation of dimsyl sodium".

[8] Romo, D.; Myers, A. I. (1992). "An asymmetric route to enantiomerically pure 1,2,3-trisubstituted cyclopropanes". J. Org. Chem. 57 (23): 6265–6270. doi:10.1021/jo00049a038.

[9] Trost, B. M.; Melvin, L. S., Jr. (1975). Sulfur Ylides: Emerging Synthetic Intermediates. New York: Academic Press. ISBN 0-12-701060-2.{{cite book}}: CS1 maint: multiple names: authors list (link)

[10] Ibarra, C. A; Rodgríguez, R. C; Monreal, M. C. F; Navarro, F. J. G.; Tesoreo, J. M. (1989). "One-pot synthesis of β-keto sulfones and β-keto sulfoxides from carboxylic acids". J. Org. Chem. 54 (23): 5620–5623. doi:10.1021/jo00284a043.

[11] Swenton, J. S.; Anderson, D. K.; Jackson, D. K.; Narasimhan, L. (1981). "1,4-Dipole-metalated quinone strategy to (±)-4-demethoxydaunomycinone and (±)-daunomycinone. Annelation of benzocyclobutenedione monoketals with lithioquinone bisketals". J. Org. Chem. 46 (24): 4825–4836. doi:10.1021/jo00337a002.

[12] Isibashi, H.; Okada, M.; Komatsu, H.; Ikeda, M. S. (1985). "A New Synthesis of Substituted Cyclopentenones by Olefin Cyclization Initiated by Pummerer Reaction Intermediates". Synthesis. 1985 (6/7): 643–645. doi:10.1055/s-1985-31290. S2CID 95643470.

[13] Hakomori, S.-I. (1964). "A Rapid Permethylation of Glycolipid, and Polysaccharide Catalyzed by Methylsulfinyl Carbanion in Dimethyl Sulfoxide". J. Biochem. 55 (2): 205–208. doi:10.1093/oxfordjournals.jbchem.a127869.

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